Coloring method for plastics



Feb. 14, 1950 H. M. coLLlNs CLORING METHOD FOR PLASTICS Filed oct. 29, 194e Patented Feb. 14, 1950 2,497,346 COLORING METHOD 'FOR PLASTICS Henry M. Collins, Vaughan,

signor to Reliable Pl astics Company,

Ontario, Canada, as-

Limited,

Toronto, Ontario, Canada Application October 29, 1946, Serial No. 706,388

3 Claims.

This invention relates to a method of adding and incorporating colouring materials to nonporous plastic materials soluble or softenable by low boiling point organic liquids.

By colouring materials is meant, any materials which are added to plastics for the purposes of colouring, rendering opaque or rendering translucent the final plastic materials and this term is meant to include such colours as the dyes and pigments themselves, the

l only in certain specic cases, because of the fact opacifying agents themselves and any mixtures.

of dyes, pigments and opacifying agents which may be added to impart special colouring o1" toning characteristics to the final plastic product. By non-porous plastic materials is meant all types of plastic materials which are non-porous in character when they are in finely divided form prior to a forming operation which may be perfor-med upon them to produce plastic products;

and by low boiling point organic liquids is meant all liquids which may be classed as organic compounds pressure are below 200 F. approximately.

The above deiinitions are given by way of explanation and to avoid confusion in the'f-ollowing specification4 and it is desired that these meanings will be given to the above terms wherever they occur within the body of the folf lowing specification and claims.

Heretofore, it has been the general practice and whose boiling points at normal to colour, tint or opacity thermoplastic moulding '1 powders which are capable of being used in compounded form in standard injection moulding machines, by means of organic and inorganicV dyes, pigments and so forth and to add these substances to the plastic mass during a milling or sheeting process which is carried out on polished steel milling rolls, or in the type of equipment known as a Banbury mixer. process is comparable to the kneading of dough, the heat of the rollers causing softening of the plastic until it is possible to knead the dyes and pigments into the mass in much the same way that ilour is kneaded into. bread dough. This process is necessarily cumbersome and slow in` comparison with most mass production methods,"

but heretofore it has been the only known method of thoroughly mixing the plastic mass and colouring material sufciently intimately to ensure a clear, uniformly coloured moulded product, free from blemishesviand faults.

Another known method that is very restricted in scope entails the addition of colouring materials to the monomeric charge before the This ucts by the use of this that most colouring materials have a depressing actionupon the polymerization of plastic monomers fand it has in most cases been found impossible to achieve satisfactory polymeric prodmethod.

Various suggestions have been made for eliminating the necessity of the above mentioned milling process, which is, although effective, relatively costly, requires cumbersome equipment, and might be represented as forming a bottleneck in the preparati-on of finished thermoplastic moulding powders, and the operation of milling represents a relatively large percent of the cost of the finished moulding powder.

It has been suggested, for instance, to grind the plastic material to a fine mesh, add an excess of powdered dye and other powdered colouring materials to the finely divided charge and to mixthe whole mass in a tumbler. In this manner the fine particles of added colour become evenly distributed over the surfaces of the finely divided particles of plastic material. The action of tumbling builds up an electrostatic charge on the plastic particles causing a very strong adherence and an even distribution of the colouring agent over the surface of the particles. Products moulded from powder prepared in this manner, however, are dull in appearance, show streaks',

and are in general quite inferior to plastic items of the charge, of course, could only be dispersed and not dissolved by the use of such solvents. Furthermore, the length of time and heating necessary to drive off Aafsuiiicient quantity of the solvents used vfrom the finished moulding powder was found to more than makeup for This sugthe time and labour saved inthe elimination of the milling process.'

A- further d'imculty en.v

counteredv in'jthe putting into' practice of thisl suggestion was 'the difficulty of spraying the dis,-

' solved colour charge into the tumbling mass of plastic is iine ground plastic particles'. I t was found that the inorganic and/ or dispersed parts' of the colouring material, since v n it was not completely polymerized. I This method is practical, however, dissolved inthe solvent, would lodgein the jets.

and block the spray equipment; and that the rate of spraying had therefore to be very carefully controlled and a frequent cleaning of the liquid lines and jets was necessary. Finally the results achieved, although better than those obtained according to the rst suggested method, were hardly comparable to those obtainable. from. the. already mentioned milling process.

I have now found that all the above mentioned difliculties may be overcome in a surprisingly simple, novel, eiiicient and unexpected manner,

by finely pulverizing the moulding material and forming a substanti-ally homogeneousmixture of said material with finely divided colouring ma.- terial, to obtain a mass of similar characteristics to that mentioned in the first suggestion above. This mass is agitated and a finely divided spray of liquid, having a relatively low boiling point and and at least some solvent power for the plastic material itself, and preferably but not necessarily solvent. power for the organic colouring,l material present, is injected over a relatively short periodi of` time and the whole resultant mass is then subjected. to. an agitation in the presence of. a stream of hot air orv non-reactive gasv to evaporate. thesolvent. A coloured moulding material' results which. produces moulded products having colour properties at least as good as those produced when using moulding powders prepared. by the milling process. Where the liquid also has a solvent action on the colouring material, a very intimate thoroughly tinted moulding. powder results. and the. colouring material permeates the moulded plastic article to-form a substantially. homogeneous coloured moulding. When the liquidv has only anaction onthe plastic a somewhat longer processing is requiredf'or equivalent results-` Agitation of. the charge during the, proceasy to measure the actual amount of liquid added since the apparatus is connected directly to the bulk supply, and the actual amount required will vary according to other conditions such as temperature and air jet Velocity. In any case the liquid, being transient to the moulding compositions, need not be accurately measured'.. Since the heat lost: in vapourizing the solvent constitutes an operating expense, it will all cases be desirable to use as little liquid as possible and once again just how little may be used is a thing which must be determined in any given case by actualexperience.

Suitable apparatus for carrying out this process is described in co-pending application Serial No. 687,302 filed July 3l, 1946, and consists of a tumbler equipped with an especially designed injector whereby it is possible to inject a stream of gas or liquid or mixtures of gas and liquid into finely divided powders while at the same time providing' for thek escape of exhaust gases without allowing escapeof the powder charge. While this type of apparatus is' particularly desir-able for the purpose of the present invention, any apparatus which provides for agitation of the charge, injection of atomize'd spray, and exhaustion of excess gases without involving substantial losses of the powder charge will be suitable.

The degree of. fineness of the moulding powder for purposes oi the invention has a large bearing. on the nal result achieved because the fact is the ner the grind, the more completely even a final colour is obtained. However, for the purpose ofeconomyitis preferable to form a balance essbesides ensuring a. complete treatment of all the particlesin thecharge, prevents any tendency to form. cakes or lumps While the. plastic particles are in a. softened state, and preserves thev free flowing characteristics necessary,v in. using the product as. av moulding powder..

The eiectI on the individual particles seems to bee-.that a softening. of. those particles,.f.or. which theintroduced liquid hasa. softening power, occurs. Where only. the. plasticv particles are. softened, a bleeding of theparticle to partly envelope the surrounding colour particles occurs,.which, on removalof the. liquid, leaves the=plastic and colour particlesinrmadherence. Where both particles arey softened, there is an inter-diffusionbetween. the; particles',.and. a much` firmer and. more complete bond unites the. particles on evaporation. of the liquid.. Since: the liquid is. injected in nely divided. form, usually in a gas. stream, andaconstamt-agitation is. carried out, thereisneverv more.

liquid. present. than is justrequiredto effect. the.

above. process of softening and adherence. or inter-diffusion, (which process willv be, hereinafter referred to as. inter.adhesion). The, subsequent drying operation removes. the solvent; be-

between the iineness of grind and shortness of. the process time and grinding time; For economical results, I prefer to use` a grind which is somewhere between 20 and 100 mesh.

Suitable temperatures for the removal of the organic liquid will of. course. Vary depending on the type. of plastic used, the volatility of the organic liquid used, and the. economic bal-ance between length of time available for the process andthe cost offproducing gases of higher. temperforefanyconsolidationof the plastic particles can.

occur. and itis a simple. matter tov determine in any specific: casejust how long to continue the.. treatment to. obtain the best. results. v Suitable. times of treatment for; someV of. the commoner typesof plastic. are indicated in the examples given below.' The details4 concerning the. injec.4m tiorr. of: fluid.. is expressed. in terms of time. of: treatment'rather. thanin. quantity of liquidaddedi; becausev ini` apparatus particularly of. the-type: de.- scribed in. my coLpending application.l Serial. No; 687,302, filed July 31, 1946, it is` generally not ature. for the purpose.. I have generally found that somewhere between the range of 250 and 400,cr F. is suitable, but in special cases temperatures outside this range are desirable.

The dry coloured charge produced by the above process is ideal for moulding purposes and the colour cannot to any extent be mechanically removed from the particles. Therange of colours possible is limited only by the colouring materials available and may be. accurately controlled to reproduce any colour or hue orr depth of shade, within very accurate limits.

Whereas the above process isi applicable to any nonporous plastic moulding powder which is at least partially soluble in a low boiling point organic solvent, it has been found particularly adapted to use. in the colouring of the following materials: polystyrene polymethyl methacrylate, polymethylacrylate, polyvinyl chloride-acetate, polyvinyl acetate, polyvinyl acetals, cellul'ose acetate, ethyl cellulose, and polyethylene.

Dyes which may be' used are almost without li'mit'but the most eiTective ones including pigmentsV are the heat stable, neutral,v complex, organic; high tinting' types normally found in the following classes:

Hansa. and. benzidine. types v Yellow Lithol-ruhine-calcium lakes, tol.- uidine .basefdyes.-,. barium ton-- ers and lakes Red and all the intermediate colours. The. only re quirements are that the dye must -be heat stable,v

power white of similar'chemical neutrality is equally satisfactory.

The low boiling organic liquids injectedinto the coloured mass will of course vary depending v 15 through exhaust ports I8 to exhaust pipe I4 and upon the particular plastic moulding powdervin use and the solubility characteristics of the. dye stuff. Generally speaking, I have found thatfor most purposes a mixture of methyl alcohol and methyl acetate ranging between 20 and 80% methyl alcohol, and mixtures of methyl alcohol and methyl-ethylketone are particularly suitable when using the more common types of moulding materials. Generally speaking, the only qualification necessary for such solvents are that they have at least some dissolving power or softening power with respect to the` plastic material being used. Choice of a particular solvent will generally depend on availability and cost.

My invention will be more `fully understood from the following detailed description with reference to the accompanying' drawing which illustrates one embodiment of an apparatus particularly adapted for process. The apparatus, which is fully described in the above mentioned previous application, consists essentiallyT of' a tumbler IIl which is rotatably mounted about massive vbushings II, and rotatable by suitable power means (not shown). Passing through the centre of the bushings II and protruding into the interior of the tumbler I are tubular members I2 which house a series of double concentric pipes I3, and exhaust pipes I4.

The tubular members terminate in a series ofv spray nozzles I5, which are adapted to project va ne spray of gas borne atomizedliquid into the tumbler I0. Shields I6 and I1 control the shape of the jets, and exhaust gases enter the exhaust pipes I4 through exhaust ports I8.

the carrying out of my mixture of liquids is introduced into the tumbler I0 by the nozzles I5. In this connection the tubular members I3 include the 'pipa-members I3a through which compressed air may be passed s to the nozzles I5 andwhich run concentrically inside the tubular members I3 4to define anfannular space I3b through which the liquid may be passed. l

The tumbling operation plus the action of the l0 jets of spray, causes a violent agitation of the mass of plastic particles and-the organic liquid droplets act on the particles of plastic and their adhering particles'of colouring material in the manner described above. The excess air escapes the escape of particles 'of plastic etc. is prevented by the action `of the jets of spray as described in the abovernentioned copending application.

" When all the liquiz-dvhas been added,ilhot air or" necting the exhaust pipes I4 to a condenser, and

a heat exchanger may be installed to recover ythe latent heat of evaporation.

The dry powder remaining in the tumbler I0 is evenly coloured andfree ilowing, and will produce coloured mouldedproducts of a character as good as or superior'to products made from milled moulding powders. f

`Relative amounts ofthe various materials used, may be slightly in excess of that used in the milling process, and the length of time for the various operationsdepends on the solvents used l and thetemperature of the gases -used-for evap-z oration purposes.- v-

The following chart is given as an indication 40 of suitable operatingquantities and times for producing coloured moulding powders from-several of the more common varieties of plastics, and in some of the more common colours. The list is not intended to be in any manner exhausillustration only. It is a simple matter for an experienced operator to determine from experi-I ment in conformity with the examples described, ideal times of operation under any given condi- To carry out the process according to my :intions for other cases outside the specic ones vention using the above apparatus, a mixture of shown.

liramplez I Spray s Drying Colour Charge, Parts per 100 parts plastic olventgigmposl' Remarks 1 Time Temp. -Time Temp.

Y Minutes F. Minutes F. 0.075 part phthalocyanine blue, 0.2 part 10 I100 1:3 methylacetate: i 1,5 `350 Clean, free-Howing,

Titanium Dioxide, 0.2 part Zinc Stearate. methanol. colourwell-secured. 0.05 part Plitlialocyanine green, 0.2 part l0 l00 ..--.do y 15 350 I Do;

Medium Chrome Green, 0.1 part Hansa Yellow, 0.2 part Titanium Dioxide, 0.2 part Zinc Stearate. 0.07 part Calco Condensation Orange, 0.02 ..do l5' 350 Do.

part Lithol Rubine Red, 0.2 part Titav -v y nium Dioxide, 0.2 part Zinc Stearate. 1 0.08 part benzidine yellow, 0.2 part Tita- 100 .--do l5 350' vDol m'um Dioxide, 0.2 part Zinc Stearate.l l f finely pulverized .plastic moulding powder .l and powdered colouring material with or without added opacifying agents, which has been intimately mixed in a previous operation, such as by tumbling, is introduced into the tumbler I0, and the tumbler is set in motion. A finely divided r l Finely divided i--firriesh polystyrene, was tum-I i bled for 35 minutes in a conventional barrel turnbler at a rate of 23-27 R. P. M. with well mixed, cosmetic grind dye shot in the proportion mentioned above and was treated by the .process according to the invention according to the times atomized spray of low boiling organic liquid or 'I and temperatures indicated.

tive or limitative, and is given. for purposes ofv mmmnt v wthimthe; enclosure. withparticlesmf. nely d:L-.

I i vided; colouring material tmformiasubstantially Finely dviddi 20-100' mesh 01211111056 ctiei homogeneous; mixture-.othe charge andthecol- M .Stflowz crystaiimoulding-Lnowder wasiusediand During 1;1;L1;e,;.ia1,1 3nd,. during the tumbling Opthefresultingmasss Wasstneated' accorilng to the 5 eration distributing thnoughout said. mixture a. inventimrasindicatedzbelowi:A finely. divided.- loweboiling, point. organic liquid C 1V Cha P s Spray -Dnszingf per 100 partslplstc. Solvcnmomposition Remarks Time Temp; Time. Tempz j Minutes F. Same as-.ExampIe-IL l0r 140 3'.l.lvIethanol:.A.cetone-. 32. 300 C1ean,. freeiowing; Colour' brilliant;

' f l evenandtrue'.

Eamplelm J winch has solventl power` for at least the plastici material, to provideinteradhesion ofthe plastic'- Fll'ely" divided. Zit-90' mesfr green' ethyl 081111'- partici'es of' the charge and'l the particles ofA they 105'y M. S fl'OW m'OUld'hg' POWdeI Was USB and. colouring` materia-l"A introduced, andi lastly evapthe resulting mass was treated according tothe' oratingfsaidmw-boiiing pointorganic liquid'while.

inventionasindicated"below: 29? tumbling continues and before consolidation of.l

O1 Ch P ts *i Spray Drying'y cour argc, ar J per. loupartpimc. Solvent,. Composition Remarks Time Temp... Time` Temp.

-Minutes. "EL Minutes 'F. i Same as Example I.... 11' 175' 2`:1'y Methanol: Methyl la. 400 Clleailitand Eree=EloWing;iGblour,excel- Acetate. en

aus said. plastic particles occursi by reasonv of. the

Emamplam solvent: action of the lowJ--looillfig point organic, Finely divided 20-80 meslrzpolystyreneawas used liquid. y and' theresulting. mass. was treated according to 2i.. The; method. of colouringJ a. charge of pultlieinventionas-indicatecl'belozwfr verized non-porous plas-tic material as. claimed in.

A l spray y n Drying colourlgigs Hanlon Solvent, Composition. f Remarks` Time TempiA Timef Tempi *Y `]\IiiiutesrV Fl 142i. 350. Glear,nonopaque colours.

SameasExampletBexceptfno 10dd :.113 methylacetate: .In-ethanol Minutes s F l5 Titanium Dioxide.`

claim 1 in which the' evaporating step is carried Exam le A p 5 outbyintroducing'a'stream-of'gas into theenclo- Finely divided' 20`-8U' mesh methylmethacrylatej Sura wasused'landresultingmass was treated accord- 3; The meth-0dn of; colouring a gharge of puling.tothefinventionas.indicatedbelow: veri'zed non-porous plastic material as claimed in C. I, CH P t Spray I Drying.

0 our arge. Br S per 100 parts plastic Solvent, Composition A Remarks Time Temp. Tlme Temp.

f .Minutes "1?.` A.itlinuifes F. Same as Example L 13 190 52:1 Methanol: Methyl' l2 420` Free-owingand dry'. Colour: excelf Ethyl Ketone. lent s l My process enables the production of moulding "claim 1 in which the evaporating step is carried powders of any desired' colourontint' or' opacity out by introducing astream of gasA intothe enat a unitv cost which iszonlyafraction. of that closure: at a temperature in the range between entailed in. usingi previously known processes, 60 250 andi400i".. and which, by the:use oftl-'ie apparatus described, eliminates the necessity for the heavy and eX- pensive capital equipment previously necessary REFERENCES CITED for producing coloured moulding powders of Sm- The following referencesare of; record in the ilar characteristics... .@5 ma of this. patent;

HENRY ML COLLINS.

What I claim as my invention is: U1 n I Y 1-. A methodo colouring acharge ofipulverized. TED STATES PTENTS non-porous plastic vmaterial within an enclosure Number Name Date which comprises the stepsi'ottumblingtlsie'charge .A1-,399,542` Walsh Feb.. 2.8, 19.33' 

1. A METHOD OF COLOURING A CHARGE OF PULVERIZED NON-POROUS PLASTIC MATERIAL WITHIN AN ENCLOSURE WHICH COMPRISES THE STEPS OF, TUMBLING THE CHARGE WITHIN THE ENCLOSURE WITH PARTICLES OF FINELY DIVIDED COLOURING MATERIAL TO FORM A SUBSTANTIALLY HOMOGENEOUS MIXTURE OF THE CHARGE AND THE COLOURING MATERIAL, AND DURING THE TUMBLING OPERATION DISTRIBUTING THROUGHOUT SAID MIXTURE A FINELY DIVIDED LOW-BOILING POINT ORGANIC LIQUID WHICH HAS SOLVENT POWER FOR AT LEAST THE PLASTIC 